CN106853436B - Molybdenum-based composite coating and preparation method thereof - Google Patents
Molybdenum-based composite coating and preparation method thereof Download PDFInfo
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- 238000000576 coating method Methods 0.000 title claims abstract description 141
- 239000011248 coating agent Substances 0.000 title claims abstract description 133
- 229910052750 molybdenum Inorganic materials 0.000 title claims abstract description 79
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 title claims abstract description 77
- 239000011733 molybdenum Substances 0.000 title claims abstract description 75
- 239000002131 composite material Substances 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 75
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 72
- 229910021332 silicide Inorganic materials 0.000 claims abstract description 45
- FVBUAEGBCNSCDD-UHFFFAOYSA-N silicide(4-) Chemical compound [Si-4] FVBUAEGBCNSCDD-UHFFFAOYSA-N 0.000 claims abstract description 45
- 239000000758 substrate Substances 0.000 claims abstract description 37
- CJNBYAVZURUTKZ-UHFFFAOYSA-N hafnium(IV) oxide Inorganic materials O=[Hf]=O CJNBYAVZURUTKZ-UHFFFAOYSA-N 0.000 claims abstract description 28
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims abstract 7
- 239000000463 material Substances 0.000 claims description 92
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical group CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 30
- 238000005245 sintering Methods 0.000 claims description 30
- 238000000034 method Methods 0.000 claims description 27
- 238000002156 mixing Methods 0.000 claims description 27
- 230000003647 oxidation Effects 0.000 claims description 26
- 238000007254 oxidation reaction Methods 0.000 claims description 26
- 239000006255 coating slurry Substances 0.000 claims description 24
- 238000000498 ball milling Methods 0.000 claims description 23
- 239000011230 binding agent Substances 0.000 claims description 22
- 239000003960 organic solvent Substances 0.000 claims description 18
- 238000004321 preservation Methods 0.000 claims description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 15
- 239000002202 Polyethylene glycol Substances 0.000 claims description 15
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 15
- 229920001223 polyethylene glycol Polymers 0.000 claims description 15
- 239000002966 varnish Substances 0.000 claims description 15
- 229910001182 Mo alloy Inorganic materials 0.000 claims description 12
- 239000007809 chemical reaction catalyst Substances 0.000 claims description 12
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 11
- 229910020968 MoSi2 Inorganic materials 0.000 claims description 10
- 229910033181 TiB2 Inorganic materials 0.000 claims description 7
- 230000003064 anti-oxidating effect Effects 0.000 claims description 7
- 150000004820 halides Chemical class 0.000 claims description 6
- 125000005843 halogen group Chemical group 0.000 claims description 5
- 230000035939 shock Effects 0.000 abstract description 12
- 239000010410 layer Substances 0.000 description 59
- 235000006708 antioxidants Nutrition 0.000 description 58
- 239000000843 powder Substances 0.000 description 41
- 239000002002 slurry Substances 0.000 description 27
- 238000012360 testing method Methods 0.000 description 20
- IJKVHSBPTUYDLN-UHFFFAOYSA-N dihydroxy(oxo)silane Chemical compound O[Si](O)=O IJKVHSBPTUYDLN-UHFFFAOYSA-N 0.000 description 18
- 239000011651 chromium Substances 0.000 description 15
- 239000002344 surface layer Substances 0.000 description 14
- 229910045601 alloy Inorganic materials 0.000 description 13
- 239000000956 alloy Substances 0.000 description 13
- 230000003068 static effect Effects 0.000 description 13
- 229910052593 corundum Inorganic materials 0.000 description 12
- 239000010431 corundum Substances 0.000 description 12
- 239000011324 bead Substances 0.000 description 10
- 239000003054 catalyst Substances 0.000 description 10
- 230000008569 process Effects 0.000 description 9
- 238000005507 spraying Methods 0.000 description 9
- 238000001035 drying Methods 0.000 description 7
- 238000000227 grinding Methods 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 6
- 238000004140 cleaning Methods 0.000 description 6
- 239000011521 glass Substances 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 229910052710 silicon Inorganic materials 0.000 description 6
- 239000007921 spray Substances 0.000 description 6
- 229910052715 tantalum Inorganic materials 0.000 description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 5
- 238000011049 filling Methods 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 238000011056 performance test Methods 0.000 description 5
- 238000005488 sandblasting Methods 0.000 description 5
- 239000010703 silicon Substances 0.000 description 5
- 229910016006 MoSi Inorganic materials 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 238000002149 energy-dispersive X-ray emission spectroscopy Methods 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 229910052758 niobium Inorganic materials 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 239000006104 solid solution Substances 0.000 description 3
- 230000003746 surface roughness Effects 0.000 description 3
- 238000012876 topography Methods 0.000 description 3
- 229910052721 tungsten Inorganic materials 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- YXTPWUNVHCYOSP-UHFFFAOYSA-N bis($l^{2}-silanylidene)molybdenum Chemical compound [Si]=[Mo]=[Si] YXTPWUNVHCYOSP-UHFFFAOYSA-N 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- 230000001680 brushing effect Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 229910052681 coesite Inorganic materials 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 229910052906 cristobalite Inorganic materials 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 238000007733 ion plating Methods 0.000 description 2
- 238000001755 magnetron sputter deposition Methods 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 229910021343 molybdenum disilicide Inorganic materials 0.000 description 2
- 238000005498 polishing Methods 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 239000003870 refractory metal Substances 0.000 description 2
- 239000004576 sand Substances 0.000 description 2
- 150000003377 silicon compounds Chemical class 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 238000005475 siliconizing Methods 0.000 description 2
- 238000007613 slurry method Methods 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 229910052682 stishovite Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910052905 tridymite Inorganic materials 0.000 description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 2
- OBOSXEWFRARQPU-UHFFFAOYSA-N 2-n,2-n-dimethylpyridine-2,5-diamine Chemical compound CN(C)C1=CC=C(N)C=N1 OBOSXEWFRARQPU-UHFFFAOYSA-N 0.000 description 1
- 229910000951 Aluminide Inorganic materials 0.000 description 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 229910014299 N-Si Inorganic materials 0.000 description 1
- 229910008423 Si—B Inorganic materials 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N SnO2 Inorganic materials O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001069 Ti alloy Inorganic materials 0.000 description 1
- 229910008253 Zr2O3 Inorganic materials 0.000 description 1
- 229910007948 ZrB2 Inorganic materials 0.000 description 1
- CPTCUNLUKFTXKF-UHFFFAOYSA-N [Ti].[Zr].[Mo] Chemical compound [Ti].[Zr].[Mo] CPTCUNLUKFTXKF-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical compound [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- LGLOITKZTDVGOE-UHFFFAOYSA-N boranylidynemolybdenum Chemical compound [Mo]#B LGLOITKZTDVGOE-UHFFFAOYSA-N 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- FLVFLHZPYDNHJE-UHFFFAOYSA-N chloro hypochlorite;hafnium Chemical compound [Hf].ClOCl FLVFLHZPYDNHJE-UHFFFAOYSA-N 0.000 description 1
- -1 compound silicate Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000001066 destructive effect Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000002241 glass-ceramic Substances 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 230000009545 invasion Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum oxide Inorganic materials [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052914 metal silicate Inorganic materials 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000005121 nitriding Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 238000007750 plasma spraying Methods 0.000 description 1
- 239000011253 protective coating Substances 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- PBCFLUZVCVVTBY-UHFFFAOYSA-N tantalum pentoxide Inorganic materials O=[Ta](=O)O[Ta](=O)=O PBCFLUZVCVVTBY-UHFFFAOYSA-N 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 238000004506 ultrasonic cleaning Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/14—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to metal, e.g. car bodies
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/24—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials for applying particular liquids or other fluent materials
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/50—Multilayers
- B05D7/52—Two layers
- B05D7/54—No clear coat specified
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D1/00—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D2202/00—Metallic substrate
- B05D2202/30—Metallic substrate based on refractory metals (Ti, V, Cr, Zr, Nb, Mo, Hf, Ta, W)
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D2451/00—Type of carrier, type of coating (Multilayers)
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- Wood Science & Technology (AREA)
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Ceramic Products (AREA)
- Powder Metallurgy (AREA)
Abstract
The invention provides a molybdenum-based composite coating, which comprises: the molybdenum substrate is compounded on the silicide bottom layer on the surface of the molybdenum substrate; the silicate outer layer is compounded on the surface of the silicide bottom layer; the bottom silicide layer is prepared from the following main components: 5 to 12 wt% of W, 2 to 7 wt% of Cr, 0.3 to 6 wt% of B, B2O3Or B4C, 0.5-7 wt% of HfO2(ii) a The silicate outer layer is prepared from the following main components: 3 to 18 wt% of Mo, 0.5 to 5 wt% of W, 0.5 to 3 wt% of Nb, 1 to 5 wt% of HfO2. The application also provides a preparation method of the molybdenum-based composite coating. Experimental results show that the composite coating can provide antioxidant protection for more than 100 hours at 1700 ℃, and thermal shock performance reaches 1120 times, 1260 times, 1211 times and 1151 times at room temperature to 1800 ℃.
Description
Technical Field
The invention relates to the technical field of coatings, in particular to a molybdenum-based composite coating and a preparation method thereof.
Background
Molybdenum belongs to refractory metals, has the advantages of high melting point and high strength, and is applied to a plurality of fields of aerospace, chemical industry, metallurgy, medical appliances and the like. However, molybdenum and its alloy will undergo severe destructive oxidation under high temperature aerobic environment to cause failure and damage, which severely limits the use of molybdenum and its alloy under high temperature environment. The surface of the molybdenum and the molybdenum alloy is coated with the anti-oxidation coating, so that the mechanical property of the alloy can be kept to the maximum extent, and meanwhile, the anti-oxidation temperature of the molybdenum alloy is greatly increased, and the method is an economic and effective protection means. At present, high-temperature oxidation resistant coatings comprise silicide coatings, aluminide coatings, heat-resistant alloy coatings and the like, and the working temperature and the oxidation resistance of molybdenum can be improved to a certain degree.
The chinese patent No. 201110383828.6 describes a method for producing a coating by a three-step in-situ reaction synthesis method, which comprises the steps of firstly introducing nitrogen into a substrate at a high temperature to nitridize the substrate, then embedding at a high temperature for siliconizing, and finally embedding at a high temperature for boriding to obtain an oxidation-resistant coating of Mo-N-Si-B system. The Chinese patent with the application number of 201310180081.3 firstly carries out the tungsten infiltration treatment on the surface of the molybdenum substrate which is pretreatedThen carrying out nitriding treatment and finally siliconizing at high temperature to obtain the Mo-W-N-Si silicide coating. Chinese patent application No. 201410733680.8 introduces a main composition: 15-20 wt% of Al, 3-5 wt% of Ni, 2-3 wt% of W, MoSi21.5-3 wt% of Cr, 0.5-0.8 wt% of Cr and the balance of Si, and is prepared by a vacuum slurry method. The Chinese patent with the application number of 201410208597.9 discloses a Hf-Y oxide coating, which is formed by mixing hafnium oxychloride and yttrium chloride in a proper proportion, dissolving the mixture in an n-propanol solution, brushing the mixture on the surface of a molybdenum substrate, then placing the molybdenum substrate in a muffle furnace to bake at the temperature of about 400 ℃, and brushing and sintering the mixture for 15-30 times. The Chinese patent with application number of 201510441949.X discloses that potassium-doped molybdenum is used as a heating element substrate material, and element diffusion reaction is carried out on reaction powder, wherein the reaction powder comprises 10-30 wt% of silicon, 5-10 wt% of at least one of boron, aluminum, chromium and tungsten powder and the balance of aluminum oxide, and the surface of the heating element substrate is embedded in the reaction powder to prepare a coating molybdenum heating element.
In addition, the silicide protective coating is prepared on the surface of molybdenum by a slurry burning method by Jiazhong and the like. Shoulelen et al sintered MoSi on the surface of molybdenum by vacuum sintering method2-ZrB2And (4) coating. The Toede shows that a silicon-aluminum coating is prepared on the surface of molybdenum by using a magnetron sputtering technology. The WangAn adopts an atmospheric plasma spraying method and an in-situ chemical vapor deposition method to prepare a molybdenum disilicide coating and a molybdenum disilicide/molybdenum boride composite coating on the surface of the molybdenum. Preparation of ZrO on molybdenum substrate by adopting slurry method such as Mach impact2And SnO2A glass-based oxidation resistant coating. In addition, the king soldier prepared an Ir coating on a molybdenum substrate using a double glow ion plating process.
In the coating materials described in the above patents and documents, the embedding method for preparing the coating is harsh in process requirements and difficult to control; magnetron sputtering has high requirements on equipment and poor economy; the brush coating-sintering method is simple and easy to implement and easy to control, but the prepared Hf-Y oxide coating has short protection time on a substrate. The double glow ion plating method is still in the research stage at present, the prepared Ir coating is expensive in cost, and the test life is only 60s (2000 ℃). As mentioned above, there is still a lack of a coating material that can be used at 1600 ℃ or higher, has a long life, is low cost, and is easy to implement and control, and a method for preparing the same.
Disclosure of Invention
The invention aims to provide a molybdenum-based composite coating, which can greatly improve the working temperature and the antioxidant effect of a molybdenum substrate.
In view of the above, the present application provides a molybdenum-based composite coating, including: the molybdenum substrate is compounded on the silicide bottom layer on the surface of the molybdenum substrate; the silicate outer layer is compounded on the surface of the silicide bottom layer;
the bottom silicide layer is prepared from the following components:
5 to 12 wt% of W, 2 to 7 wt% of Cr, 0.3 to 6 wt% of B, B2O3Or B4C, 0.5-7 wt% of HfO2；
At least one of the following components: 1 to 5 wt% of Mo, 0.5 to 1.5 wt% of Ta, 1 to 4 wt% of Fe, 0.5 to 1.5 wt% of S, 0.2 to 0.5 wt% of TiB21 to 5 wt% of SiC and 1 to 5 wt% of ZrO2Or 1 to 5 wt% of Zr, MoSi2；
The balance of Si;
the silicate outer layer is prepared from the following components:
3 to 18 wt% of Mo, 0.5 to 5 wt% of W, 0.5 to 3 wt% of Nb, 1 to 5 wt% of HfO2；
At least one of the following components: 0.2 to 2 wt% of Ta or an oxide thereof, 0.2 to 1.5 wt% of V, 0.7 to 1.5 wt% of La or an oxide thereof, 0.3 to 2.2 wt% of Y or an oxide thereof, 0.2 to 1 wt% of BaO, 0.7 to 4 wt% of Ge or an oxide thereof, 1 to 7 wt% of Zr or an oxide thereof, 1 to 5 wt% of B or an oxide thereof;
the balance being Si.
Preferably, in the silicide bottom layer, the content of Cr is 5.5-7 wt%; the B, B2O3Or B4The content of C is 3-6 wt%; the HfO2The content of (B) is 5.5-7 wt%.
Preferably, in the silicate outer layer, the content of Mo is 16-18 wt%, and the content of W is 3.5-4 wt%.
Preferably, the thickness of the composite coating is 80-130 μm.
Preferably, the material of the molybdenum substrate is pure molybdenum or molybdenum alloy.
The application also provides a preparation method of the molybdenum-based composite coating, which comprises the following steps:
A) mixing the components of the bottom silicide layer of claim 1 to obtain a first oxidation resistant material; mixing the components of the silicate outer layer of claim 1 to provide a second antioxidant material; mixing the first antioxidant material, the organic solvent, the binder and the reaction catalyst, and performing ball milling to obtain first coating slurry; mixing the second antioxidant material, the organic solvent, the binder and the reaction catalyst, and performing ball milling to obtain second coating slurry;
B) coating the first coating slurry on the surface of the pretreated molybdenum substrate, and carrying out heat preservation after sintering to obtain a silicide bottom layer;
C) and coating the second coating slurry on the surface of the silicide bottom layer, and carrying out heat preservation after sintering to obtain a silicate outer layer.
Preferably, in the step of obtaining the first coating slurry, the organic solvent is ethyl acetate or absolute ethyl alcohol, the binder is nitro varnish or polyethylene glycol, and the reaction catalyst is halide; in the step of obtaining the second coating slurry, the organic solvent is ethyl acetate or absolute ethyl alcohol, the binder is nitro varnish or polyethylene glycol, and the reaction catalyst is halide.
Preferably, the volume ratio of the first antioxidant material to the organic solvent is 1: (1-2), wherein the mass ratio of the first antioxidant material to the nitro varnish is 1: (0.5-2), wherein the mass ratio of the first antioxidant material to the polyethylene glycol is 1: (0.01-0.06), wherein the mass ratio of the first antioxidant material to the halide is 1: (0.003-0.03); the volume ratio of the second antioxidant material to the organic solvent is 1: (1-2), wherein the mass ratio of the second antioxidant material to the nitro varnish is 1: (0.5-2), wherein the mass ratio of the second antioxidant material to the polyethylene glycol is 1: (0.01-0.06), wherein the mass ratio of the second antioxidant material to the halide is 1: (0.003-0.03).
Preferably, in the step B), the sintering temperature is 1300-1550 ℃, and the vacuum degree is more than 0.1 Pa; the heat preservation time is 15-60 min.
Preferably, in the step C), the sintering temperature is 1350-1550 ℃, the vacuum degree is greater than 0.1Pa, and the heat preservation time is 15-60 min.
The application provides a molybdenum-based composite coating, which comprises a silicon compound bottom layer and a silicate outer layer, and the application obtains a ceramic-glass phase outer layer with high melting point and high density by adopting two groups of coating materials with different proportions, so that the working temperature and the antioxidant effect of the molybdenum substrate are greatly improved; furthermore, the different components of the silicide bottom layer and the silicate outer layer enable the coefficient of thermal expansion of the formed coating to present gradient change, the silicide bottom layer and the molybdenum base material are metallurgically bonded, the firm bonding of the coating and the base material is ensured, and the coating can work in a rapid cooling and heating environment. Experimental results show that the composite coating can provide antioxidant protection for more than 100 hours at 1700 ℃, and thermal shock performance can reach 1120 times, 1260 times, 1211 times and 1151 times at room temperature to 1800 ℃.
Drawings
FIG. 1 is a flow chart of the composite coating preparation process of the present invention;
FIG. 2 is a surface microtopography of a composite coating prepared in example 1 of the present invention;
FIG. 3 is a cross-sectional micro-topography of a composite coating prepared in example 1 of the present invention;
FIG. 4 is an EDS analysis of the coating after static testing at 1800 ℃ for 50h for the composite coating prepared in example 1 of the present invention;
FIG. 5 is a photograph of a ceramic-glass phase formed on the surface of the composite coating prepared in example 1 of the present invention after being tested at 1800 ℃ for 50 hours;
FIG. 6 is a photograph of the cross-sectional profile of the composite coating prepared in example 3 of the present invention after static testing at 1800 ℃ for 30 h.
Detailed Description
For a further understanding of the invention, reference will now be made to the preferred embodiments of the invention by way of example, and it is to be understood that the description is intended to further illustrate features and advantages of the invention, and not to limit the scope of the claims.
The embodiment of the invention discloses a molybdenum-based composite coating, which comprises: the molybdenum substrate is compounded on the silicide bottom layer on the surface of the molybdenum substrate; the silicate outer layer is compounded on the surface of the silicide bottom layer;
the bottom silicide layer is prepared from the following components:
5 to 12 wt% of W, 2 to 7 wt% of Cr, 0.3 to 6 wt% of B, B2O3Or B4C, 0.5-7 wt% of HfO2；
At least one of the following components: 1 to 5 wt% of Mo, 0.5 to 1.5 wt% of Ta, 1 to 4 wt% of Fe, 0.5 to 1.5 wt% of S, 0.2 to 0.5 wt% of TiB21 to 5 wt% of SiC and 1 to 5 wt% of ZrO2Or 1 to 5 wt% of Zr, MoSi2；
The balance of Si;
the silicate outer layer is prepared from the following components:
3 to 18 wt% of Mo, 0.5 to 5 wt% of W, 0.5 to 3 wt% of Nb, 1 to 5 wt% of HfO2；
At least one of the following components: 0.2 to 2 wt% of Ta or an oxide thereof, 0.2 to 1.5 wt% of V, 0.7 to 1.5 wt% of La or an oxide thereof, 0.3 to 2.2 wt% of Y or an oxide thereof, 0.2 to 1 wt% of BaO, 0.7 to 4 wt% of Ge or an oxide thereof, 1 to 7 wt% of Zr or an oxide thereof, 1 to 5 wt% of B or an oxide thereof;
the balance being Si.
The application provides a molybdenum-based composite coating, it is including compound silicate skin, silicide bottom and the molybdenum substrate in proper order, this application makes bottom and molybdenum substrate can form good metallurgical bonding through adjustment molybdenum substrate skin and bottom component and content, guarantees that composite coating does not drop, and the composite coating that forms simultaneously forms high melting point, high fine and close pottery-glass looks skin, makes the operating temperature and the anti-oxidant effect of molybdenum substrate promote by a wide margin.
The amount of W in the silicide underlayer is 5 to 12 wt%, in certain embodiments 7 to 12 wt%, and illustratively 7, 7.8, 8.1, 8.5, 9.0, 9.8, 10.0, 10.7, 11.2, or 11.6 wt%.
The content of Cr is 2 to 7 wt%, and in an embodiment, the content of Cr is 5.5 to 7 wt%, and for example, the content of Cr may be 6.0 wt%, 6.2 wt%, 6.5 wt%, 6.8 wt%, or 7 wt%.
The B, B2O3Or B4The content of C is 0.3-6 wt%, in the embodiment, the B, B2O3Or B4C content of 2.5 to 6 wt%, for example, the B, B2O3Or B4The content of C is 2.5 wt%, 3.2 wt%, 3.7 wt%, 4.3 wt%, 4.7 wt%, 5.0 wt%, 5.4 wt% or 6 wt%.
The HfO2Is 0.5 to 7 wt%, in an embodiment, the HfO2In an amount of 2 to 7 wt%, illustratively, the HfO2Is present in an amount of 2.6 wt%, 3.0 wt%, 3.2 wt%, 3.8 wt%, 4.5 wt%, 5.2 wt%, 6.8 wt% or 7.0 wt%.
In the silicide underlayer, the W, Cr, B or compound thereof, HfO2And Si, and 1-5 wt% of Mo, 0.5-1.5 wt% of Ta, 1-4 wt% of Fe, 0.5-1.5 wt% of S, 0.2-0.5 wt% of TiB21 to 5 wt% of SiC and 1 to 5 wt% of ZrO2Or Zr and 1-5 wt% MoSi2At least one of (1). Among the above elements, one component may be added, or a plurality of components may be added, and may be selected according to the properties of a specific silicide underlayer to be formed. In specific embodiments, the Mo content is 1.5 to 4.0 wt%, and more specifically, the Mo content is 1.8 wt%, 2.4 wt%, 3.0 wt%, 3.2 wt%, 3.5 wt%, or 4.0 wt%. In a specific embodiment, the content of Ta is 0.8 wt% to 1.2 wt%. In a specific embodiment, the content of Fe is 1.5-3.0 wt%. In a specific embodiment, the content of S is 1 to 1.5 wt%. In specific embodiments, the TiB2Is contained in an amount of 0.2 wt%, 0.3 wt%, 0.4 wt% or 0.5 wt%. In a specific embodiment, the content of SiC is 2.5 to 4.0 wt%, specifically, the content of SiC is 2.8 wt%, 3.2 wt%, 3.5 wt%, or 3.8 wt%. In a specific embodiment, the ZrO2In an amount of 1.8 to 4.2 wt%, and specifically, the ZrO 22Is 2.0 wt%, 2.2 wt%, 2.8 wt%, 3.4 wt%, 3.8 wt% or 4.0 wt%. In a specific embodiment, the MoSi2The content of (a) is 1.6 wt% to 4.2 wt%, specifically, the MoSi is2Is 2.0 wt%, 2.4 wt%, 2.8 wt%, 3.4 wt% or 4.0 wt%.
More activating elements are added in the bottom layer of the coating, which has the function of forming high silicide, and decomposing at high temperature to form simple substance silicon and low silicon compounds, and the silicon element jumps to the surface layer to provide antioxidant elements for the surface layer, thereby playing the role of a 'reserve layer'; the function of part of the non-metallic elements is to corrode the surface of the molybdenum and molybdenum alloy substrate at high temperature, so that the specific surface area of the substrate is increased, the reaction degree of the coating and the alloy is increased, and the binding force of the coating and the alloy is increased. In addition, partial strengthening elements or compounds are added to improve the strength of the coating, adjust the elastic modulus of the coating, improve the thermal shock resistance of the coating and improve the environmental adaptability of the coating.
In the formed silicate outer layer, the content of Mo is 3-18 wt%, in specific embodiments 6-18 wt%, in certain specific embodiments 10-17 wt%, in particular 12 wt%, 15 wt%, 16.2 wt%, 17 wt% or 18 wt%.
The amount of W is 0.5 to 5 wt%, in some embodiments 2 to 5 wt%, in some embodiments 3.5 to 5 wt%, and in particular 3.5 wt%, 3.8 wt%, 4.0 wt%, 4.2 wt%, or 4.8 wt%.
The Nb content is 0.5-3 wt%, in some embodiments, 1-2.5 wt%, specifically, 1.2 wt%, 1.5 wt%, 2.0 wt%, or 2.2 wt%.
The HfO2In an amount of 1 to 5 wt%, in some embodiments, the HfO2In an amount of 1.2 to 3.8 wt%, and in certain embodiments, the HfO2The content of (B) is 1.8-2.5 wt%.
In the silicate outer layer, the W, Mo, Nb, HfO2And Si, in addition, 0.2-2 wt% of Ta or its oxide, 0.2-1.5 wt% of V, 0.7-1.5 wt% of La or its oxide, 0.3-2.2 wt% of Y or its oxide, 0.2-1 wt% of BaO, 0.7-4 wt% of Ge or its oxide, 1-7 wt% of Zr or its oxide and 1-5 wt% of B or its oxide can be added according to the formed silicate outer layer; among the above elements, one component may be added, or a plurality of components may be added, and may be selected according to the properties of the specific silicate outer layer formed. In a specific embodiment, the Ta or oxide content is 2 wt% to 2.8 wt%. In a specific embodiment, the content of V is 1.2-1.5 wt%. In specific embodiments, the La or the oxide thereof is contained in an amount of 0.8 to 1.5 wt%, and more specifically, the La or the oxide thereof is contained in an amount of 0.9 wt%, 1.2 wt%, 1.4 wt%, or 1.5 wt%. In a specific embodiment, the content of Y or an oxide thereof is 0.8 to 2.2 wt%, and specifically, the content of Y or an oxide thereof is 1.0 wt%, 1.2 wt%, 1.8 wt%, or 2.0 wt%. In a specific embodiment, the content of BaO is 0.4 to 0.9 wt%. In a specific embodiment, the content of Ge or an oxide thereof is 1.2-3.6 wt%, and in a specific embodiment, the content of Ge or an oxide thereof is 2.0-3.0 wt%. In a specific embodiment, the Zr or the oxide thereof is present in an amount of 3 to 6.8 wt%, specifically, the ZrO is present in an amount of2Is 3.2 wt%, 4.5 wt%, 4.8 wt%, 5.6 wt%, 6.5 wt% or 6.8 wt%. In specific embodiments, the content of B or an oxide thereof is 1.2 wt% to 4.5 wt%, and specifically, the content of B or an oxide thereof is 1.4 wt%, 1.6 wt%, 2.8 wt%, 3.4 wt%, or 4.2 wt%.
Part of the composite coating meets high-temperature environment in the atmosphere and the outer layer is heated and oxidizedAfter the silicide of the metal element is oxidized, the metal silicate with high melting point can be formed, and SiO2A ceramic-glass phase is formed, and the high-temperature stability of the surface layer is improved; part of nonmetal and metal oxide can reduce SiO2The softening temperature of the surface layer, and the thermal shock resistance of the surface layer is improved. In addition, the addition of part of the metal elements and the formation of silicide play a role in adjusting the thermal expansion coefficient of the surface layer.
The application also provides a preparation method of the molybdenum-based composite coating, the preparation flow is shown in fig. 1, and specifically, the preparation method of the molybdenum-based composite coating comprises the following steps:
A) mixing the components of the bottom silicide layer of claim 1 to obtain a first oxidation resistant material; mixing the components of the silicate outer layer of claim 1 to provide a second antioxidant material; mixing the first antioxidant material, the organic solvent, the binder and the reaction catalyst, and performing ball milling to obtain first coating slurry; mixing the second antioxidant material, the organic solvent, the binder and the reaction catalyst, and performing ball milling to obtain second coating slurry;
B) coating the first coating slurry on the surface of the pretreated molybdenum substrate, and carrying out heat preservation after sintering to obtain a silicide bottom layer;
C) and coating the second anti-oxidation slurry on the surface of the silicide bottom layer, and carrying out heat preservation after sintering to obtain a silicate outer layer.
In the process of preparing the molybdenum-based composite coating, the preparation of raw material components in the composite coating is firstly carried out, namely, the components in the bottom layer of the silicide and the outer layer of the silicate are respectively mixed according to the proportion to respectively obtain a first antioxidant material and a second antioxidant material; and mixing the obtained first antioxidant material and the second antioxidant material with an organic solvent, a binder and a reaction catalyst respectively, and performing ball milling to obtain first coating slurry and second coating slurry respectively.
In the above process, the organic solvent serves as a carrier for adjusting the viscosity and fluidity of the coating slurry, thereby improving the coating uniformity of the slurry and realizing rapid drying and curing. The organic solvent is preferablyAnd is selected from absolute ethyl alcohol or ethyl acetate. The binder is preferably nitro varnish or polyethylene glycol, the reaction catalyst is preferably halide, and the halide is NH4One or more of Cl, NaF, NaCl, KF and KCl. The volume ratio of the first antioxidant material to the organic solvent is 1: (1-2), wherein the mass ratio of the first antioxidant material to the nitro varnish is 1: (0.5-2), preferably 1: (0.8-1.2), wherein the mass ratio of the first antioxidant material to the polyethylene glycol is 1: (0.01-0.06), wherein the mass ratio of the first antioxidant material to the halide is 1: (0.003-0.03); the ratio of the second antioxidant material to the additive is the same as the range of the first antioxidant material, and in a specific embodiment, the ratio of the first antioxidant material to the additive may be the same as or different from that of the second antioxidant material, and the application is not particularly limited. The rotation speed of the ball milling is 150-400 r/min, and the ball milling time is 3-12 h; in a specific embodiment, in the process of preparing the first coating slurry, the rotation speed of ball milling is 150-300 r/min, the ball milling time is 8-10 h, in the process of preparing the first coating slurry, the rotation speed of ball milling is 180-320 r/min, and the ball milling time is 8-10 h.
Prior to applying the first coating slurry, the molybdenum substrate is preferably subjected to a pretreatment, which is a technical means well known to those skilled in the art and is not particularly limited herein, and the pretreatment may be, for example, grinding, sand blasting, acid washing or vacuum annealing. The material of the molybdenum substrate is pure molybdenum or a molybdenum alloy, wherein the molybdenum alloy is a molybdenum alloy known to those skilled in the art, and the material is not particularly limited in this application.
According to the invention, the first coating slurry is coated on the surface of the molybdenum substrate, and the temperature is kept after the coating slurry is sintered to obtain the silicide bottom layer. The sintering temperature is 1300-1550 ℃, and the vacuum degree is more than 0.1 Pa; the heat preservation time is 15-60 min; in a specific embodiment, the sintering temperature is 1350-1500 ℃, and the heat preservation time is 45-60 min. After the silicide bottom layer is obtained, the second antioxidant coating slurry is coated on the surface of the silicide bottom layer, and the silicide bottom layer is obtained by heat preservation after sintering. The sintering temperature is 1300-1550 ℃, and the vacuum degree is more than 0.1 Pa; the heat preservation time is 15-60 min; in a specific embodiment, the sintering temperature is 1350-1500 ℃, and the heat preservation time is 45-50 min.
In the process of sintering, partial metal and silicon in the ingredients of the bottom layer and the outer layer generate solid solution, and partial metal and metal oxide react with the silicon to generate silicide and silicate, so that a complex mixture of the solid solution, the silicide and the silicate is formed. Mo which is a refractory metal different from metals such as Ta and Nb and MoSi which is a main silicide of Mo2Has a greatly different coefficient of linear expansion (CET) (5.2X 10 Mo)-6/℃，MoSi2Is 8.1 × 10-6and/K), therefore, different from Nb and Ta metal and alloy oxidation resistant coatings, the requirements on the modified components and structural layer design (layer number and structural layer thickness) of the molybdenum and molybdenum alloy oxidation resistant coatings are higher, otherwise, the coating is easy to crack, peel or have surface protrusion and other quality defects due to improper thermal expansion coefficient matching or poor component solid solution.
The high-temperature oxidation-resistant coating material for molybdenum and molybdenum alloy and the preparation method thereof have the characteristics and advantages that: two groups of coating materials with different proportions are used, and a secondary overlapping sintering method is adopted to prepare the composite coating. The high-temperature lower surface of the composite coating can form a highly densified and stabilized complex ceramic-glass film layer, so that the problem of rapid volatilization failure at more than 1500 ℃ commonly existing in molybdenum and molybdenum alloy silicide coatings is solved, and the working temperature of the coating is effectively increased; meanwhile, the different component designs of the bottom layer and the surface layer lead the thermal expansion coefficient of the coating to show gradient change, thereby solving the problem that the molybdenum and molybdenum alloy traditional silicide coating is caused by the MoSi of the coating main body2The thermal expansion coefficient of the coating is too large to cause the fatal defects of peeling, stripping, cracking and the like of the coating, so that the performance of the coating is effectively improved; in addition, in the process of superposition sintering, slight thermal diffusion between the surface layer and the bottom layer and between the bottom layer and the alloy can be realized by adjusting the sintering process, so that metallurgical-grade combination is formed, the binding force between the coating interlayer structure and the coating and the alloy is improved, and the coating is prevented from being opened under the working condition of alternating cold and heatCracking and even peeling off, further improving the practical working capacity of the coating.
For further understanding of the present invention, the following detailed description of the composite coating and the preparation method thereof are provided in connection with examples, and the scope of the present invention is not limited by the following examples.
Example 1
1) Two groups of high-temperature oxidation resistant materials are respectively as follows:
5 wt% of W, 2 wt% of Cr, 2 wt% of B, 1.2 wt% of Ta, 1 wt% of Mo, HfO2Is 2 wt%, ZrO23 wt%, SiC 2.8 wt%, and the balance Si;
7.2 wt% of Mo, 2.2 wt% of W, 3 wt% of Nb, 2.2 wt% of Y, HfO23 wt%, BaO 1 wt%, Ta 2 wt%, B3 wt%, and the balance Si;
mixing the two groups of materials uniformly according to a proportion, grinding the materials into powder with a particle size of not more than 300 meshes by using a planetary ball mill respectively, and filling the powder into different containers;
2) cleaning the surface of a molybdenum base material by using a sand blasting method (the equipment is a long-air brand GS-943 suction type dry sand blasting machine, 80-mesh white corundum sand), then soaking in absolute ethyl alcohol for 30min, and airing for later use;
3) adding nitrovarnish (Zhejiang paint Co., Ltd., Baotai brand nitrovarnish) with the powder mass of 80 wt% and NaF with the powder mass of 3 wt% into the antioxidant material of the first group respectively as a binder and a catalyst, adding ethyl acetate with the powder volume of 2 times as a carrier, uniformly mixing, ball-milling for 12 hours at the rotating speed of 150r/min by using corundum beads to prepare slurry, uniformly coating the slurry on the surface of a molybdenum substrate, baking, sintering at the temperature of 1380 ℃ and the vacuum degree of more than or equal to 0.1Pa, and preserving heat for 60 minutes to prepare an antioxidant coating bottom layer with the thickness of 65-80 mu m;
4) adding nitro varnish (Zhejiang paint Co., Ltd.) accounting for 120 wt% of the powder and KF accounting for 2 wt% of the powder into the oxidation resistant material in the second group respectively as a binder and a catalyst, adding ethyl acetate accounting for 2 times of the powder volume as a carrier, mixing uniformly, ball-milling with corundum beads at a rotating speed of 200r/min for 10h to prepare slurry, uniformly coating the slurry on the surface of the bottom layer of the oxidation resistant coating, drying, sintering at a temperature of 1550 ℃ and a vacuum degree of not less than 0.1Pa, and keeping the temperature for 50min to prepare a surface layer of the oxidation resistant coating with a thickness of about 25-35 μm, finally forming a composite oxidation resistant coating with an overall thickness of 90-120 μm, wherein FIG. 2 is a surface micro-topography diagram of the composite coating prepared in the embodiment 1 of the invention, FIG. 3 is a cross-section micro-topography diagram of the composite coating prepared in the embodiment 1 of the invention, and FIGS. 2 and 3 are compact, a molybdenum coating prepared by using two oxidation resistant materials has a typical structure, particles, a typical composite dispersion structure, a three-layer structure, and a loose bottom layer and a certain bonding force with a honeycomb-like alloy coating and a certain diffusion effect of improving the alloy coating.
5) The method for testing the oxidation resistance of the oxidation-resistant coating comprises the following steps: the molybdenum sample is subjected to a high temperature test at 1800 ℃, and the test method comprises the following steps: electrifying the sample by using a copper electrode, and heating the sample by using the heat generated by the resistance of the copper electrode; the method comprises the steps of measuring the temperature of a sample by using a B17MR1SBSF type two-color integrated temperature measuring instrument (the temperature measuring range is 600-2100 ℃, the temperature measuring precision is +/-15.75 ℃) of Raytek corporation in America, controlling the current passing through the sample by using an FP23 temperature control meter of SHIMADEN corporation in Japan to further control the temperature (+/-10 ℃), and testing until black spots appear on the surface of the sample, wherein the coating fails; EDS analysis was performed on the failed test pieces with an instrument model Zeiss SUPRA55, the results are shown in FIG. 4, FIG. 4 is EDS analysis of the composite coating prepared in example 1 of the present invention after static test at 1800 ℃ for 50 h; as can be seen from FIG. 4, after the anti-oxidation coating is statically tested for 50h at 1800 ℃, the oxygen element in the coating is increased, but the oxygen element content in the base material is very low, which proves that the coating has good anti-oxidation effect on the base material.
The coating is subjected to a 1700 ℃ and 1800 ℃ high-temperature oxidation resistance test, as shown in fig. 5, the test result shows that a dark black glass-ceramic phase protective layer can be formed on the surface of the coating at high temperature, so that the invasion of oxygen can be effectively blocked, the coating has good static and thermal shock oxidation resistance, and the result is shown in table 1.
TABLE 1 comprehensive performance test data sheet for antioxidant coating
Example 2
1) Two groups of high-temperature oxidation resistant materials are respectively as follows:
7 wt% of W, 7 wt% of Cr and B2O32.5 wt%, Fe 3 wt%, S1 wt%, Mo 5 wt%, HfO24 wt% of SiC, 3 wt% of MoSi22.8 wt%, the balance being Si;
12 wt% of Mo, 3.5 wt% of W, 1 wt% of Nb and 1 wt% of Y2O30.8 wt%, HfO23 wt%, BaO 0.7 wt%, V1.2 wt%, B1 wt%, and the balance Si;
mixing the two groups of materials uniformly according to a proportion, grinding the materials into powder with a particle size of not more than 300 meshes by using a planetary ball mill respectively, and filling the powder into different containers;
2) grinding the surface of a TZM alloy (molybdenum zirconium titanium alloy) base material by using No. 400 abrasive paper until the surface is bright and free from foreign matter adhesion, soaking for 30min by using absolute ethyl alcohol, and airing for later use;
3) adding 150 wt% of nitro varnish (Zhejiang paint Co., Ltd.) and 3 wt% of NaF (NaF) as a binder and a catalyst respectively into the antioxidant material, adding ethyl acetate 2 times the volume of the powder as a carrier, uniformly mixing, ball-milling for 8 hours at a rotating speed of 150r/min by using corundum beads to prepare slurry, uniformly coating the slurry on the surface of a TZM substrate, baking, sintering at a temperature of 1360 ℃ and a vacuum degree of more than or equal to 0.1Pa, and preserving heat for 60 minutes to prepare an antioxidant coating bottom layer with a thickness of about 75-85 mu m;
4) adding nitro varnish (Zhejiang paint Co., Ltd., Baotai brand nitro varnish) accounting for 120 wt% of the powder mass and KF accounting for 3 wt% of the powder mass into the antioxidant material in the second group respectively as a binder and a catalyst, adding ethyl acetate accounting for 2 times of the powder volume as a carrier, uniformly mixing, ball-milling for 8 hours at a rotating speed of 180r/min by using corundum beads to prepare slurry, uniformly coating the slurry on the surface of the bottom layer of the antioxidant coating, baking, sintering at a temperature of 1500 ℃ and a vacuum degree of more than or equal to 0.1Pa, and keeping the temperature for 45 minutes to prepare the surface layer of the antioxidant coating, wherein the thickness of the surface layer of the antioxidant coating is about 20-30 mu m, and the finally molded composite antioxidant coating has the integral thickness of 95-.
Example 3
1) Two groups of high-temperature oxidation resistant materials are respectively as follows:
10 wt% of W, 4 wt% of Cr and B42 wt% of C, HfO24 Wt%, Ta 1 Wt%, Mo 5 Wt%, S1.2 Wt%, TiB20.5 wt% of ZrO23 wt%, the balance being Si;
15 wt% of Mo, 3.5 wt% of W, 0.5 wt% of Nb, HfO25 wt% of La2O31.2 wt%, Y1 wt%, Zr2O37 wt%, the balance being Si;
mixing the two groups of materials uniformly according to a proportion, grinding the materials into powder with a particle size of not more than 300 meshes by using a planetary ball mill respectively, and filling the powder into different containers;
2) and (3) carrying out sand blasting on the molybdenum metal base material by using a dry sand blasting machine and 300# white corundum sand until the surface is bright and free of foreign matter adhesion, the surface roughness is larger than zero and less than or equal to Ra6.3 mu m (sample plate contrast method), carrying out ultrasonic cleaning on the sample at the frequency of 20-30 KHz for 15-20 minutes, and immersing the test piece into absolute ethyl alcohol for later use after cleaning.
3) respectively adding polyethylene glycol accounting for 5 wt% of the weight of the powder and KCl accounting for 1 wt% of the weight of the powder into the antioxidant material in the first group as a binder and a catalyst, adding absolute ethyl alcohol accounting for 2 times of the volume of the powder as a carrier, uniformly mixing, ball-milling with corundum beads at a rotating speed of 200r/min for 12 hours to prepare slurry, spraying the slurry on the surface of a molybdenum base material by using a spray gun, wherein the spraying thickness is about 300 mu m, naturally drying, then sintering at a temperature of 1500 ℃, and under a vacuum degree of more than or equal to 0.1Pa, and preserving heat for 40min to prepare an antioxidant coating bottom layer with the thickness of about 60-70 mu m;
4) polyethylene glycol accounting for 5 wt% of the powder and KCl accounting for 0.5 wt% of the powder are respectively added into the antioxidant materials in the second group to serve as a binder and a catalyst, absolute ethyl alcohol accounting for 2 times of the powder in volume is added to serve as a carrier, after the mixture is uniformly mixed, corundum beads are used for ball milling for 10 hours at a rotating speed of 300r/min to prepare slurry, the slurry is sprayed on the surface of a bottom coating by a spray gun, the spraying thickness is about 150 micrometers, after the slurry is naturally dried, the slurry is sintered at a temperature of 1500 ℃ and a vacuum degree of more than or equal to 0.1Pa, the temperature is kept for 30 minutes to prepare an antioxidant coating surface layer, the thickness is about 20-30 micrometers, a picture 6 of the cross section morphology of the composite coating prepared in the embodiment 3 is obtained after static test for 30 hours at a temperature of 1800 ℃, and.
TABLE 2 antioxidant coating antioxidant performance test data sheet
Example 4
1) Two groups of high-temperature oxidation resistant materials are respectively as follows:
7 wt% of W, 5 wt% of Cr and B4C4 wt%, HfO26 wt% of Mo, 3 wt% of TiB20.5 wt% of ZrO23 wt% of MoSi24 wt%, the balance being Si;
16.2 wt% of Mo, 3.5 wt% of W, 1.2 wt% of Nb, HfO22.5 wt%, Ta 1 wt%, V1.2 wt%, Y2 wt%, Ge 2.5 wt%, B2O3Is 2 wt%, ZrO23.2 wt%, the balance being Si;
mixing the two groups of materials uniformly according to a proportion, grinding the materials into powder with a particle size of not more than 300 meshes by using a planetary ball mill respectively, and filling the powder into different containers;
2) and (3) polishing the pure molybdenum metal base material by using No. 240 and No. 500 waterproof abrasive paper until the surface is bright and free of foreign matter adhesion, the surface roughness is larger than zero and less than or equal to Ra3.2 mu m (template comparison), ultrasonically cleaning the sample at the frequency of 20-30 KHz for 15-20 minutes, and immersing the test piece into absolute ethyl alcohol for later use after cleaning.
3) respectively adding polyethylene glycol with the powder mass of 3 wt% and NH4Cl with the powder mass of 0.5 wt% into the antioxidant material of the first group as a binder and a catalyst, adding absolute ethyl alcohol with the powder volume of 1.5 times as a carrier, uniformly mixing, ball-milling with corundum beads at the rotating speed of 300r/min for 8 hours to prepare slurry, spraying the slurry on the surface of a molybdenum base material by using a spray gun, wherein the spraying thickness is about 300 mu m, naturally drying, then sintering at the temperature of 1550 ℃ and the vacuum degree of more than or equal to 0.1Pa, and preserving heat for 20 minutes to prepare an antioxidant coating bottom layer with the thickness of about 50-60 mu m;
4) adding nitro varnish accounting for 50 wt% of the powder mass and NH accounting for 0.8 wt% of the powder mass into the antioxidant material in ② th group4And Cl is used as a binder and a catalyst, absolute ethyl alcohol with the volume of 1.5 times of that of the powder is added as a carrier, after uniform mixing, corundum beads are used for ball milling for 10 hours at the rotating speed of 300r/min to prepare slurry, the slurry is sprayed on the surface of a bottom coating by a spray gun, the spraying thickness is about 200 mu m, after natural drying, the slurry is sintered at the temperature of 1550 ℃ and the vacuum degree of more than or equal to 0.1Pa, and the temperature is kept for 20 minutes to prepare an anti-oxidation coating surface layer with the thickness of about 30-50 mu m. Table 3 is a table of antioxidant performance test data of the antioxidant composite coating.
TABLE 3 antioxidant coating antioxidant performance test data sheet
| Test piece numbering | Coating thickness (μm) | Test items | Testing performance |
| 87 | 91 | Static state at 1800 DEG C | 46h |
| 88 | 86 | Thermal shock at 1800 DEG C | 669 times |
| 89 | 86 | Thermal shock at 1800 DEG C | 876 times |
| 91 | 84 | Thermal shock at 1800 DEG C | 699 times |
| 92 | 88 | Thermal shock at 1800 DEG C | 775 times |
| 93 | 87 | Static state at 1800 DEG C | 44h10min |
| 94 | 86 | Thermal shock at 1800 DEG C | 731 times |
| 95 | 86 | Static state at 1800 DEG C | 46h30min |
Example 5
1) Two groups of high-temperature oxidation resistant materials are respectively as follows:
6 wt% of W, 7 wt% of Cr and B2O33 wt%, HfO25.5 wt%, Mo 5 wt%, Ta 1 wt%, S0.6 wt%, ZrO22 wt% of MoSi2Is 5 wt%;
18 wt% of Mo, 4 wt% of W, 2 wt% of Nb, HfO25 wt% of Ta2O52 wt%, V1.5 wt%, Y2O32.2 wt%, Ge 3.4 wt%, B1 wt%, ZrO2Is 5 wt%;
mixing the two groups of materials uniformly according to a proportion, grinding the materials into powder with a particle size of not more than 300 meshes by using a planetary ball mill respectively, and filling the powder into different containers;
2) and (3) polishing the TZM alloy base material by using 240# and 500# waterproof abrasive paper until the surface is bright and free of foreign matter adhesion, the surface roughness is not more than Ra3.2 mu m (template comparison), ultrasonically cleaning the sample at the frequency of 20-30 KHz for 10-20 minutes, and immersing the test piece into absolute ethyl alcohol for later use after cleaning.
3) respectively adding polyethylene glycol with the mass of 6 wt% of powder and NaF with the mass of 0.5 wt% of the powder into the antioxidant material of the first group as a binder and a catalyst, adding ethyl acetate with the volume of 2 times of the powder as a carrier, uniformly mixing, ball-milling for 6 hours at the rotating speed of 400r/min by using corundum beads to prepare slurry, spraying the slurry on the surface of a molybdenum substrate by using a spray gun, wherein the spraying thickness is about 300 mu m, naturally drying, then sintering at the temperature of 1530 ℃ and the vacuum degree of more than or equal to 0.1Pa, and preserving heat for 12 minutes to prepare an antioxidant coating bottom layer with the thickness of about 71-82 mu m;
4) polyethylene glycol with the mass of 6 wt% of powder and KCl with the mass of 1 wt% of the powder are respectively added into the antioxidant materials in the second group to serve as a binder and a catalyst, absolute ethyl alcohol with the volume of 1.5 times of that of the powder is added to serve as a carrier, after the mixture is uniformly mixed, corundum beads are used for ball milling for 8 hours at the rotating speed of 400r/min to prepare slurry, the slurry is sprayed on the surface of a bottom coating by a spray gun, the spraying thickness is about 200 mu m, after natural drying, the slurry is sintered at the temperature of 1550 ℃ and the vacuum degree of more than or equal to 0.1Pa, heat preservation is carried out for 20 minutes to prepare an antioxidant coating surface layer, the thickness is about 25-35 mu m, and a table.
TABLE 4 antioxidant coating antioxidant performance test data sheet
| Test piece numbering | Coating thickness (μm) | Test items | Testing performance |
| 148 | 109 | Static state at 1900 deg.C | 25min |
| 149 | 106 | Static state at 1700 deg.C | 142h |
| 150 | 103 | Static state at 1700 deg.C | 141h |
| 151 | 110 | Static state at 1900 deg.C | 15min |
| 152 | 101 | Thermal shock at 1800 DEG C | 636 times of |
| 153 | 107 | Thermal shock at 1800 DEG C | 722 times of |
| 154 | 108 | Static state at 1700 deg.C | 136h |
The above description of the embodiments is only intended to facilitate the understanding of the method of the invention and its core idea. It should be noted that, for those skilled in the art, it is possible to make various improvements and modifications to the present invention without departing from the principle of the present invention, and those improvements and modifications also fall within the scope of the claims of the present invention.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (10)
1. A molybdenum-based composite coating, comprising: the molybdenum substrate is compounded on the silicide bottom layer on the surface of the molybdenum substrate; the silicate outer layer is compounded on the surface of the silicide bottom layer;
the anti-oxidation material of the silicide bottom layer is prepared from the following components:
5 to 12 wt% of W, 2 to 7 wt% of Cr, 0.3 to 6 wt% of B, B2O3Or B4C, 0.5 to 7 wt%HfO2；
At least one of the following components: 1 to 5 wt% of Mo, 0.5 to 1.5 wt% of Ta, 1 to 4 wt% of Fe, 0.5 to 1.5 wt% of S, 0.2 to 0.5 wt% of TiB21 to 5 wt% of SiC and 1 to 5 wt% of ZrO2Or 1 to 5 wt% of Zr, MoSi2；
The balance of Si;
the antioxidant material of the silicate outer layer is prepared from the following components:
3 to 18 wt% of Mo, 0.5 to 5 wt% of W, 0.5 to 3 wt% of Nb, 1 to 5 wt% of HfO2；
At least one of the following components: 0.2 to 2 wt% of Ta or an oxide thereof, 0.2 to 1.5 wt% of V, 0.7 to 1.5 wt% of La or an oxide thereof, 0.3 to 2.2 wt% of Y or an oxide thereof, 0.2 to 1 wt% of BaO, 0.7 to 4 wt% of Ge or an oxide thereof, 1 to 7 wt% of Zr or an oxide thereof, 1 to 5 wt% of B or an oxide thereof;
the balance of Si;
the molybdenum-based composite coating is prepared from two groups of coating materials with different proportions by a secondary superposition sintering method.
2. The molybdenum-based composite coating according to claim 1, wherein the content of Cr in the silicide underlayer is 5.5 to 7 wt%; the B, B2O3Or B4The content of C is 3-6 wt%; the HfO2The content of (B) is 5.5-7 wt%.
3. The molybdenum-based composite coating according to claim 1, wherein the content of Mo is 16 to 18 wt% and the content of W is 3.5 to 4 wt% in the silicate outer layer.
4. The molybdenum-based composite coating according to claim 1, wherein the composite coating has a thickness of 80 to 130 μm.
5. The molybdenum-based composite coating according to claim 1, wherein the material of the molybdenum substrate is pure molybdenum or a molybdenum alloy.
6. The method of preparing a molybdenum-based composite coating according to claim 1, comprising the steps of:
A) mixing the components of the oxidation resistant material of the silicide underlayer of claim 1 to obtain a first oxidation resistant material; mixing the components of the antioxidant material of the silicate outer layer of claim 1 to obtain a second antioxidant material; mixing the first antioxidant material, the organic solvent, the binder and the reaction catalyst, and performing ball milling to obtain first coating slurry; mixing the second antioxidant material, the organic solvent, the binder and the reaction catalyst, and performing ball milling to obtain second coating slurry;
B) coating the first coating slurry on the surface of the pretreated molybdenum substrate, and carrying out heat preservation after sintering to obtain a silicide bottom layer;
C) and coating the second coating slurry on the surface of the silicide bottom layer, and carrying out heat preservation after sintering to obtain a silicate outer layer.
7. The method according to claim 6, wherein in the step of obtaining the first coating slurry, the organic solvent is ethyl acetate or absolute ethyl alcohol, the binder is a nitro varnish or polyethylene glycol, and the reaction catalyst is a halide; in the step of obtaining the second coating slurry, the organic solvent is ethyl acetate or absolute ethyl alcohol, the binder is nitro varnish or polyethylene glycol, and the reaction catalyst is halide.
8. The method of claim 7, wherein the volume ratio of the first antioxidant material to the organic solvent is 1: (1-2), wherein the mass ratio of the first antioxidant material to the nitro varnish is 1: (0.5-2), wherein the mass ratio of the first antioxidant material to the polyethylene glycol is 1: (0.01-0.06), wherein the mass ratio of the first antioxidant material to the halide is 1: (0.003-0.03); the volume ratio of the second antioxidant material to the organic solvent is 1: (1-2), wherein the mass ratio of the second antioxidant material to the nitro varnish is 1: (0.5-2), wherein the mass ratio of the second antioxidant material to the polyethylene glycol is 1: (0.01-0.06), wherein the mass ratio of the second antioxidant material to the halide is 1: (0.003-0.03).
9. The preparation method according to claim 6, wherein in the step B), the sintering temperature is 1300-1550 ℃, and the vacuum degree is more than 0.1 Pa; the heat preservation time is 15-60 min.
10. The preparation method of claim 6, wherein in the step C), the sintering temperature is 1350-1550 ℃, the vacuum degree is greater than 0.1Pa, and the heat preservation time is 15-60 min.
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